WSC2, Barnaul, March 2003

Applications of Sampling for Theory

Pentti Minkkinen
Lappeenranta University of Technology
e-mail: Pentti.Minkkinen@lut.f
Sources of sampling error
Correct and incorrect sampling
Estimation of sampling uncertainty
Optimization of sampling procedures
Practical examples

LOT

Primary Secondary Analysis Result

sample sample

s1

s2

s3

sx
x

Propagation of errors: s x

2
s
i

Example: s x (5%) 2 (2%) 2 (1%) 2 30(%)2 5.5%

GOAL: x =
Analytical process usually contains several sampling and
sample preparation steps

SAMPLING
Art of cutting a small portion of material from a large lot and
transferring it to the analyzer
Theory of sampling (theoretical) distributions with known
properties
SLOGANS
The result is not better than the sample that it is based on
Sample must be representative
Theory that combines both technical and statistical parts
of sampling has been developed by Pierre Gy:
Sampling for Analytical Purposes, Wiley, 1998

PLANNING OF SAMPLING
1.

GATHERING OF INFORMATION

What are the analytes to be determined?

What kind of estimates are needed?
Average (hour, day, shift, batch, shipment, etc.)
Distribution (heterogeneity) of the determinand in the lot
Highest or lowest values
Is there available useful a priory information (variance estimates, unit
costs)?
Is all the necessary personnel and equipment available?
What is the maximum cost or uncertainty level of the investigation?

PLANNING OF SAMPLING
2.

DECISIONS TO BE MADE

Manual vs. automatic sampling

Sampling frequency
Sample sizes
Sampling locations
Individual vs. composite samples
Sampling strategy
Random selection
Stratified random selection
Systematic stratified selection
Training

Global
Global Estimation
Estimation Error
Error
GEE
GEE
Total Sampling Error
TSE

Total Analytical Error

TAE
Point
Point Materialization
Materialization Error
Error

Weighting Error

PME
PME

Increment
Increment DelimiDelimitation
tationError
Error

IDE
IDE

Increment
IncrementExtraction
Extraction
Error
Error

IXE
IXE

SWE

Increment
Incrementand
andSample
Sample
Preparation
PreparationError
Error

IPE
IPE

Point Selection Error

PSE

Long Range
Point Selection Error

PSE1

Fundamental
Sampling Error

FSE

Periodic
Point Selection Error

PSE2

Grouping and
Segregation Error

GSE

GEE=TSE +TAE
TSE= (PSE+FSE+GSE)+(IDE+IXE+IPE)+SWE

Error components of analytical determination according to P.Gy

Sample
Ideal
mixing
0-D

If the lot to be sampled can be mixed before sampling it can be treated

as a 0-dimensional lot. Fundamental sampling error determines the
correct sampling error and can be estimated by using binomial or
Poisson distributions as models, or by using Gys fundamental sampling
error equations.

1-D

Samples

2-D
If the lot cannot be mixed before sampling the dimensionality of the lot
depends on how the samples are delimited and cut from the lot. Autocorrelation has to be taken into account in sampling error estimation

Samples

3-D

Lot is 3-dimensional, if none of the dimensions is completely

included in the sample

Weighting error
Sample
No.
1
2
3
4
5
6
7
8
9

Mean
Sum

Concentration
mg/l

Volume
3
m

cV
g

4.58
3.71
5.20
5.71
4 .54
6.78
7.12
5.81
5.86

28.6
16.2
28.99
26.48
22.08
24.75
26.55
34.76
29.05

6.25
4.36
5.58
4.64
4.86
3.65
3.73
5.98
4.96

4.89
44.01

5.479
49.3

Weighted mean concentration:

ciVi

Vi

26.39
237.47

= 4.86 mg/l

Total emission estimate (unweighted):

3
3
M 9 c V 9 4 .89 g / m 5 .479 m 241.13

Total emission estimate (weighted):

3
3
M w 9 c w V 9 4 .86 g / m 5 .479 m 237.47 g

Weighting error (in concentration): 0.03 mg/l

Weighting error (in total emission): 3.66 g

Incorrect sample delimitation

Correct sample delimitation

v = constant 0.6 m/s

if d > 3 mm, b 3d = b0
if d < 3 mm, b 10 mm = b0
a b
c

d = diameter of largest particles

b0 = minimum opening of the
sample cutter

Correct design for proportional sampler:

correct increment extraction

Process analyzers often have sample delimitation problems

Incorrect Increment and Sample Preparation Errors

Contamination (extraneous material in sample)

Losses (adsorption, condensation, precipitation, etc.)
Alteration of chemical composition (preservation)
Alteration of physical composition (agglomeration,
breaking of particles, moisture, etc.)
Involuntary mistakes (mixed sample numbers, lack of
knowledge, negligence)
Deliberate faults (salting of gold ores, deliberate errors in
increment delimitation, forgery, etc.)

Estimation of Fundamental Sampling Error

by Using Poisson Distribution
Poisson distribution is describes the random distribution of rare
events in a given interval.
If s is the number of critical particles in sample, the standard
Deviation expressed as the number of particles is

n n

(1)

The relative standard deviation is

(2)

Example
Plant Manager: I am producing fine-ground limestone that is used
in paper mills for coating printing paper. According to their specification my product must not contain more than 5 particles/tonne
particles larger than 5 m. How should I sample my product?
Sampling Expert: That is a bit too general a question. Lets first
define our goal. Would 20 % relative standard deviation for the
coarse particles be sufficient?
Plant Manager: Yes.
Sampling Expert: Well, lets consider the problem. We could use the
Poisson distribution to estimate the required sample size. Lets see:

The maximum relative standard deviation sr = 20 % = 0.2. From

equation 2 we can estimate how many coarse particles there should be
in the sample to have this standard deviation

1
1
n 2
25
2
s r 0.2

If 1 tonne contains 5 coarse particles this result means that the primary
sample should be 25 tonnes. This is a good example of an impossible
sampling problem. Even though you could take a 25 tonne sample there
is no feasible technology to separate and count the coarse particles
from it. You shouldnt try the traditional analytical approach in controlling the quality of your product. Instead, if the specification is really
sensible, you forget the particle size analyzers and maintain the quality
of your product by process technological means, that is, you take care
that all equipment are regularly serviced and their high performance
maintained to guarantee the product quality.
Plant Manager: Thank you

P. Gys Fundamental sampling error model

1
1
Cd (

)
MS ML
2
r

Cd 3

Ms
where

if Ms << ML

a
r
= relative standard deviation
aL
Ms = sample size
ML = lot size
d = particle size (95 % top size)
aL = average concentration of the analyte in the lot
C = Sampling constant

SAMPLING CONSTANT C

C f g c
composition factor
liberation factor
size distribution factor
shape factor

f=1

f=0,524

d
f=0,5

d
f=0,1

default in most cases

Estimation of shape factor

L=d
L

L
d

max 1

Estimation of liberation factor for unliberated and

liberated particles

Estimation of size distribution factor, g

Wide size distribution (d/d0.05 > 4) default

g = 0.25

Medium distribution (d/d0.05 = 4...2)

Narrow distribution (1 < d/d0.05 < 2)
Identical particles
(d/d0.05 = 1)

g = 0.50
g = 0.75
g = 1.00

Estimation of constitution factor, c

density of critical particles
average concentration of the lot

aL
1

c
aL

aL
c 1 m

density of matrix

concentration of determinand in critical particles

Example:
A chicken feed (density = 0.67 g/cm3) contains as an average 0.05 % of an
enzyme powder that has a density of 1.08 g/cm3. The size distribution of the
enzyme particle size d=1.00 mm and the size range factor g = 0.5 could be
estimated.
Estimate the fundamental sampling error for the following analytical procedure.
First a 500 g sample is taken from a 25 kg bag. This sample is ground to a
particle size -0.5 mm. Then the enzyme is extracted from a 2 g sample by
using a proper solvent and the concentration is determined by using liquid
chromatography.
The relative standard deviation of the chromatographic measurement is 5 %.

ML =25000 g;
d = 1 mm
c = 1.08 g/cm3 ; = 100 % ; = 1
m = 0.67 g/cm3 ; aL = 0.05 % ; f = 0.5
c =2160 g/cm3
d 1= 1 mm; MS1 = 500 g ; ML1 =25000 g; g 1 = 0.5;
C 1= 540 g/cm3
sr1 = 0.033 =3.3 % (primary sample)
d 2= 0.5 mm; MS2 =2 g ; ML2 =500 g; g 2 = 0.25;
C 1= 270 g/cm3
sr2 = 0.13 =13 % (secondary sample)
sr3 = 0.05 = 5 % (analysis)
Total relative standard deviation:

st

2
s
ri 0.143 14.3 %

Analysis of Mineral Mixtures by

Using IR Spectrometry
Pentti Minkkinen a), Marko Lalloa), Pekka Stenb), and Markku J. Lehtinenc)
a)

b)

Lappeenranta University of Technology, Department of Chemical Technology, P.O. Box

20,
FIN-53851 Lappeenranta, Finland
Technical Research Centre of Finland (VTT), Chemical Technology, Mineral Processing,
P.O. Box 1405, FIN-83501 Outokumpu, Finland
c)
Partek Nordkalk Oy Ab, Poikkitie 1, FIN-53500 Lappeenranta, Finland
(Present address: Geological Survey of Finland, R & D Department/Mineralogy and
Applied Mineralogy, P.O.Box 96, FIN-2151 Espoo, Finland)

Content
Introduction
Sampling error estimation and sample
preparation
Design of calibration and test sets
Calibration (PLS)
Results

Introduction
In mineral processing it is important to know quantitatively the mineral composition of the material to be
processed
The methods presently in use time consuming
Only a few reports in literature on use of IR for mineral
analysis
Feasibility of FTIR (Nicolet Magna 560) to analyze
quantitatively mineral species associated with wollastonite
was studied

Mineral Mixture Studied

Mineral

Formula

Concentration
Range (%)

Wollastonite

CaSiO3

80 - 95

Calcite

CaCO3

1 - 10

Dolomite

CaMg(CO3)2

1 - 10

Quartz

SiO2

1 - 10

Diopside

CaMgSi2O6

1 - 10

MATERIAL PROPERTIES
NEEDED IN SAMPLING
ERROR ESTIMATION
Component

Wollastonite
Calcite
Dolomite
Quartz
Diopside
KBr

Density
g/cm3
3.0
2.8
2.86
2.65
3.3
2.75

Particle size, d.95

m
37
45
31
45
43

Design of calibration set

Mixture design for five components by using
XVERT- algorithm (CORNELL, J.A., Experiments with Mixtures, 2nd Edition, Wiley, 1990,
pp 139-227)
37 calibration and 5 validation standards

Calibration
Spectra recorded with Nicolet Magna 560 FTIR
spectrometer
Calibration with PLS1 (model calculated by using
TURBOQUANT program)

PREPARATION OF CALIBRATION
STANDARDS
1. Pure minerals (d=1mm) were ground
individually 2 min in a swing mill
2. 30 mg - 2.95 g of each mineral were carefully
weighted to obtain the designed composition
which was carefully mixed 3 min in a Retsch
Spectro Mill
3. 20 mg of the mineral mixture was carefully
weighted into 4.98 g of KBr and mixed 3 min in
a Retsch Spectro Mill
4. 200 mg of the mineral-KBr mixture was pressed
into a tablet for the IR measurement

Sampling errors of sample

preparation and IR measurement
0.2 g
Dilution factor =
= 0.004
5.0 g

Tablet Preparation:
Lot size = ML1 = 5 g
Sample size = Ms1 = 0.2 g
IR Measurement:
Lot size = ML2 = 200 mg
Sample size = Ms2 = 38% of 0.2 g = 76
mg

RESULTS
10
s r1

%
s r2

%
s rt
%

4
2
0

4
5
6
7
8
Quartz concentration (%)

FSE of quartz determination

10

s r1

0.8

%
s r2

0.7

%
s rt
%

0.6

0.5

0.4

80

82

84

86

88

90

92

Wollastonite concentration (%)

FSE of wollastonite determination

94

96

Experimental result (PLS-calibration)

QUARTZ

12

PREDICTED (%)

10
8
6
4
2
0
0

6
DESIGN (%)

Designed vs. predicted concentration

* = calibration, o = test set

10

12

WOLLASTONITE
96
94
PREDICTED (%)

92
90
88
86
84
82
80
78
76

78

80

82

84

86
88
90
DESIGN (%)

92

Designed vs. predicted concentration

* = calibration, o = test set

94

96

Conclusions
FTIR and PLS can be used for mineral analysis
Design and preparation of the calibration set
important; pure minerals hard to get and vary in
composition from deposit to deposit and also within
a deposit
Reproducible sample preparation important both
from the spectroscopic point of view and to control
the sampling error
Still difficult for a routine laboratory

Uses of Gys fundamental sampling error

model
sr of a given sample size
Minimum Ms for a required sr
Maximum d for given Ms and sr
Audit and design of multistep sampling procedures

Estimation of point selection error,

PSE
PSE is the error of the mean of a continuous lot estimated by using
discrete samples.
PSEdepends on sample selection strategy, if consecutive
values are autocorrelated. Selection options:
random
stratified random
stratified systematic.
Point selection error has two components: PSE = PSE1 + PSE2
PSE1 ... error component caused by random drift
PSE2 ... error component caused by cyclic drift
Statistics of correlated series is needed to evaluate the sampling
variance.

CONCENTRATION
CONCENTRATION

100
50
0

Random selection
0

10

15

TIME

20

25

30

100
50
0

Stratified selection
0

10

15

20

25

30

CONCENTRATION

TIME

100
50
0

Systematic selection
0

10

15
TIME

20

25

30

When sampling autocorrelated series the same number of

samples gives different uncertainties for the mean depending
on selection strategy
Random sampling:

sx

sp
n

sstr
Stratified sampling: s x
n
ssys
Systematic sampling: s
x
n

sp is the process
standard deviation,
sstr and ssys standard
deviation estimates
where the autocorrelation has been
taken into account.

Normally sp > sstr > ssys ,

except in periodic processes, where ssys may be the
largest

Estimation of PSE by variography

Variogaphic experiment: N samples collected at equal
distances
ai a L M i
, i 1, 2, , N
Heterogeneity of the
hi
aL M
process:
Variogram of heterogeneity calculated:

N j
1
Vj
hi j hi

2 N j i 1

N
, j 1,2, ,
2

To estimate variances the variogram has to be integrated (numerically

in Gys method)

0.015

0.01

0.005
0.04

0.02

0
0.02

0.01

0
0.02

0.01
0

10

15

20

25

30

35

40

45

50

SAMPLE INTERVAL

Shapes of variograms: A. Random process; B. Process with

non-periodic drift; C. Periodic process; D. Complex process

Estimation of sulfur in wastewater

stream
1

hi

0.5

0.5

10

15

20

25

30

DAYS

Heterogeneity of the process, sp = 0.282 =28.2 %

0.15

Vi

0.1

0.05

10

12

14

Sample interval (d)

Variogram of sulfur in wastewater stream

16

25

s str

sr (%)

20

s sys

15
10
5
00

10

15

Sample interval (d)

Relative standard deviation estimates, which take autocorrelation into account

Estimate the uncertainty of the annual mean, if one

sample/ week is analyzed by using systematic sample
selection
Sampling interval = 7 d ssys = 7.8 %
Number of samples/y = n =52

ssys

7.8%

1.1%
Standard deviation of the annual mean = s x
n
52
Expanded uncertainty = U 0.95 2 s x 2.2%
Process standard deviation was 28.2 %. If the number of samples is
estimated by using normal approximation (or samples are selected
completely randomly) the required number of samples is for the same
uncertainty:
s 2p (28.2%) 2
n 2
657
2
sx
(1.1%)

CONCLUSIONS
Sampling uncertainty can be, and should be estimated
If the sampling uncertainty is not known it is questionable
whether the sample should be analyzed at all
Sampling nearly always takes a significant part of the
total uncertainty budget
Optimization of sampling and analytical procedures may
result significant savings, or better results, including
scales from laboratory procedures and process sampling
to large national surveys


THANK YOU